CN114000172B - Method for trapping and reducing carbon dioxide and co-producing oxygen or chlorine - Google Patents

Method for trapping and reducing carbon dioxide and co-producing oxygen or chlorine Download PDF

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CN114000172B
CN114000172B CN202111541091.6A CN202111541091A CN114000172B CN 114000172 B CN114000172 B CN 114000172B CN 202111541091 A CN202111541091 A CN 202111541091A CN 114000172 B CN114000172 B CN 114000172B
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carbon dioxide
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CN114000172A (en
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傅大学
史佳壮
王铖宇
余时铠
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Northeastern University China
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/21—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms two or more diaphragms
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00—Carbonates of sodium, potassium or alkali metals in general
    • C01D7/10—Preparation of bicarbonates from carbonates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/23—Carbon monoxide or syngas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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    • C25B1/26—Chlorine; Compounds thereof
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
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    • C25B3/03—Acyclic or carbocyclic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
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    • C25B3/25—Reduction

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Abstract

The invention belongs to the field of energy and environment, and particularly relates to a method for capturing and reducing carbon dioxide and co-producing oxygen or chlorine. The method comprises the following three steps: (1) carbon dioxide absorption; (2) An electrolytic cell device is arranged and solution is added, wherein the electrolytic cell is divided into two or three electrode chambers by one or two ion exchange membranes, an acid solution is adopted as electrolyte in an anode chamber or an end anode chamber, an alkali solution is adopted as electrolyte in an end cathode chamber, and CO is adopted in the cathode chamber or an intermediate cathode chamber 2 Absorbing the solution. And (3) switching on a power supply to carry out electrolysis. The invention does not need to introduce CO 2 The gas can be used for preparing reduction products such as carbon monoxide, methane, ethanol or formic acid and the like, and simultaneously preparing hydrogen, oxygen or chlorine, and the technology can realize CO 2 Emission reduction and H byproduct 2 It will also promote the wide utilization of hydrogen energy. Finally, a virtuous circle which takes carbon emission reduction as a starting point and promotes energy structure transformation and upgrading is formed.

Description

Method for capturing and reducing carbon dioxide and co-producing oxygen or chlorine
Technical Field
The invention belongs to the field of energy and environment, and particularly relates to a method for trapping and reducing carbon dioxide and co-producing oxygen or chlorine.
Background
Fossil fuels have been the main source of energy, and a large amount of carbon dioxide gas is generated in the combustion process, thereby aggravating the greenhouse effect and causing global warming. The global efforts are made to reduce the emission of carbon dioxide, and China proposes 'carbon peak reaching and carbon neutralization'.
The energy structure is changed, and the problem of carbon emission can be fundamentally solved by replacing fossil energy with clean energy. Another method is carbon dioxide capture utilization. At present, the following technologies are mainly applied in the carbon capture process: absorption, adsorption, membrane separation, hydrate-based separations, cryogenic distillation, and the like.
The chemical absorption method has the advantages of mature technology, large absorption capacity and the like, and is generally considered as the most economical and practical CO 2 A capture technique. The method firstly utilizes a liquid absorbent to absorb CO from the flue gas 2 . The absorbent is then regenerated by stripping, heating or reducing the pressure, with the release of pure CO 2 Typical adsorbents include Monoethanolamine (MEA), diethanolamine (DEA) and potassium carbonate. Prepared pure CO 2 Can be further applied as a chemical raw material. One of the uses is to prepare CO or organic matter by diaphragm electrolysis.
The electroreduction of CO disclosed in patents CN110117794A, CN105297067A and CN108286054A 2 The method for preparing CO or formate is to use pure CO 2 Introducing the gas into a three-chamber or two-chamber electrolytic cell, and preparing a corresponding product through electrochemical reduction; a large number of research papers have been published which also require the introduction of pure CO 2 A gas. These processes all require CO 2 By combining the trapping techniques, i.e. first producing pure CO 2 A gas.
Patent CN110983357A discloses a three-chamber diaphragm electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide and simultaneously producing chlorine and bicarbonate as byproducts, which comprises introducing carbon dioxide gas into organic composite electrolyte, dissolving a large amount of CO 2 The organic electrolyte is introduced into the cathode chamber to generate CO gas, and the anode chamber generates chlorine gas, but the method cannot obtain pure hydrogen.
Disclosure of Invention
In order to overcome the defects, the invention provides a method for collecting carbon dioxide, reducing the carbon dioxide to generate reduction products such as carbon monoxide, methane, ethanol, formic acid and the like, and co-producing oxygen or chlorine, and can also co-produce hydrogen by arranging a three-chamber electrolytic cell.
The technical scheme for realizing the invention is carried out according to the following steps:
(1) Carbon dioxide absorption: absorbing CO2 gas in the flue gas by using a solution containing hydroxide or/and carbonate to form an absorption solution; the hydroxide or/and carbonate is preferably potassium hydroxide or/and potassium carbonate, and the above is used for absorbing CO in the flue gas to improve the absorption rate 2 The solution of the gas may contain an absorption accelerator such as piperazine, and after absorption, the hydroxide and/or carbonate in the solution may be converted into bicarbonate.
CO in the flue gas 2 The gas has any concentration and absorbs CO in the flue gas 2 The concentration of bicarbonate in the absorption solution generated after the gas is more than 0.1mol/L.
(2) The electrolytic cell apparatus was set up and the solution was added using one of two methods:
the method a comprises the following steps: the middle of the electrolytic cell device is provided with a cation exchange membrane, the electrolytic cell is divided into two reaction chambers, namely a cathode chamber and an anode chamber, the cathode chamber is provided with a cathode connected with a negative electrode of a power supply, the anode chamber is provided with an anode connected with a positive electrode of the power supply, the absorption solution is added into the cathode chamber, and the acid solution is added into the anode chamber.
The method b: the electrolytic cell device is provided with two ion exchange membranes, and the electrolytic cell is divided into three reaction chambers; an anode connected with the positive pole of a power supply is arranged in a reaction chamber at one end, and the reaction chamber is called an end anode chamber; a cathode connected with a negative electrode of a power supply is arranged in the reaction chamber at the other end and the reaction chamber in the middle, and the two reaction chambers are respectively called an end cathode chamber and a middle cathode chamber; the ion exchange membrane between the end anode chamber and the middle cathode chamber is a cation exchange membrane, and the ion exchange membrane between the end cathode chamber and the middle cathode chamber is a cation exchange membrane or an anion exchange membrane; adding alkali solution into the end cathode chambers, adding absorption solution into the middle cathode chambers, and adding acid solution into the end anode chambers.
The acid solution can be one or a mixture of several of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid in any proportion; the alkali solution can be one or more of aqueous solution of alkali metal hydroxide, aqueous solution of alkali metal carbonate, aqueous solution of alkali metal bicarbonate, aqueous solution of ammonia, ammonium carbonate, ammonium bicarbonate, ammonium sulfate and other ammonium salts in any proportion.
The cathode arranged in the cathode chamber in the method a and the cathode arranged in the middle cathode chamber in the method b are one of Cu, zn, pb, ag, au and Pt metal electrodes or alloys between the Cu, zn, pb, ag, au and Pt metal electrodes. The anode in the anode chamber in the method a, the anode in the end anode chamber in the method b and the cathode in the end cathode chamber are inert electrodes which do not participate in the reaction, and preferably, the anode chamber or the anode in the end anode chamber adopts an iridium oxide coated titanium electrode, irO 2 ·Ta 2 O 5 Coating a titanium electrode, a glassy carbon electrode or a graphite electrode; the cathode in the end cathode chamber adopts one of a titanium electrode, a stainless steel electrode, a graphite electrode, a Cu, zn, pb, ag, au and Pt metal electrode or an alloy of the titanium electrode, the stainless steel electrode and the graphite electrode.
(3) In the method a, the gas generated in the anode chamber and the gas or/and liquid generated in the cathode chamber are respectively collected, in this case, the gas generated in the anode chamber is pure oxygen or chlorine (if the acid solution contains hydrochloric acid, the gas is chlorine, otherwise, the gas is oxygen), the gas or/and liquid generated in the cathode chamber is a reduction product, and carbon monoxide, methane, ethanol, formic acid, methanol and the like can be included according to the electrode material used in the cathode chamber.
In method b, the gases produced in the end cathode chambers, the end anode chambers and the gases or/and liquids produced in the intermediate cathode chambers are collected separately. In this case: the end anode chamber is the same as the gas generated in method a; the intermediate chamber and the cathode chamber of process a produce the same reduction product and may include carbon monoxide, methane, ethanol, formic acid, methanol, etc. depending on the electrode material used in the intermediate chamber; pure hydrogen gas is produced in the end cathode chamber.
In process b, the electrolysed solution in the end cathode compartments can be recovered for use in the absorption of CO from the flue gases in step (1) 2 A gas. Further, the following method may be employed: continuously introducing the absorption solutionIntroducing the solution into the middle cathode chamber, separating the reduction product from the solution electrolyzed in the middle cathode chamber, introducing the solution into the end cathode chambers, and using the solution electrolyzed in the end cathode chambers for absorbing CO in the flue gas in the step (1) 2 Gas, which enables recycling between the solution in the middle cathode compartment, the solution in the end cathode compartments and the carbon dioxide absorbing solution.
When the electrolytic cell is used for electrolysis, the temperature range is controlled to be 0-100 ℃. The electrolysis voltage is not lower than the electrolysis voltage of water.
KCl and K can be added into the solution of each reaction chamber in the method a and the method b 2 SO 4 、KClO 4 Phosphate, sodium chloride, sodium sulfate, KHSO 4 、NaHSO 4 One or more of sodium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, quaternary ammonium salt, choline chloride, propylene carbonate, N-methylpyrrolidone, diethyl carbonate and acetonitrile are used as supporting electrolytes.
In the method b, one or two anodes in the end anode chamber are adopted; when one anode is arranged in the end anode chamber, the anode is simultaneously connected with the anodes of two power supplies, and the cathodes of the end cathode chamber and the middle cathode chamber are respectively connected with the cathode of one power supply; when two anodes are arranged in the end anode chamber, the two anodes are respectively connected with the anodes of two different power supplies, and the cathodes of the two different power supplies are respectively connected with the cathode of the end cathode chamber and the cathode of the middle cathode chamber.
Compared with the prior art, the invention has the characteristics and beneficial effects that:
(1) By using the electrolysis device of the invention, pure CO is not required to be introduced 2 Gas, directly to absorb CO in flue gas 2 The absorption solution is used as a raw material to prepare carbon monoxide, methane, ethanol, formic acid, methanol and the like.
(2) Can treat CO-containing 2 Any concentration of exhaust gas; oxygen or pure chlorine can also be co-produced as a by-product; pure hydrogen can also be produced using method b, which can be used as a clean energy source.
(3) With the approach of carbon peak-reaching and carbon neutralization targets, the technology can realize CO 2 The emission is reduced,by-production of H 2 It will also promote the wide utilization of hydrogen energy. Finally, a virtuous circle which takes carbon emission reduction as a starting point and promotes energy structure transformation and upgrading is formed.
Drawings
FIG. 1 shows an electrolytic cell apparatus used in example 1.
FIG. 2 shows an electrolytic cell apparatus used in examples 2 to 6.
FIG. 3 shows an electrolytic cell apparatus used in examples 7 and 8.
Wherein: 1-cathode, 2-anode, 3-cation exchange membrane, 4-anion exchange membrane, 5-anode chamber, 6-cathode chamber, 7-end anode chamber, 8-middle cathode chamber, 9-end cathode chamber, 10-CO 2 An absorption device.
Detailed Description
The scheme of the invention is described in detail below with reference to examples:
example 1
(1) Carbon dioxide absorption: absorbing gas containing 12% of carbon dioxide by adopting a potassium carbonate solution, wherein the concentration of potassium bicarbonate after absorption reaches 0.5mol/L.
(2) Setting an electrolytic cell device and adding a solution: as shown in figure 1, the electrolytic cell device is provided with a cation exchange membrane 3 in the middle, the electrolytic cell is divided into two reaction chambers, namely a cathode chamber 6 and an anode chamber 5, the cathode chamber is provided with a cathode 1 connected with the negative pole of a power supply, and the anode chamber is provided with an anode 2 connected with the positive pole of the power supply. An iridium oxide coating titanium electrode is adopted as an anode chamber electrode; the electrode of the cathode chamber adopts a Cu electrode.
1mol/L sulfuric acid is put into the anode chamber, and CO is absorbed in the step (1) 2 The solution of (2) was passed into the cathode chamber at a rate of 30 ml/min.
(3) The power supply of the electrolytic cell device is switched on for electrolysis, and the electrolysis temperature is 20 ℃. After the power is switched on, pure O is generated in the anode chamber 2 (ii) a The cathode compartment produces the reduction product methane.
Example 2
(1) Carbon dioxide absorption: potassium carbonate solution is adopted to absorb gas containing 3 percent of carbon dioxide, and the concentration of potassium bicarbonate after absorption reaches 0.1mol/L.
(2) Setting an electrolytic cell device and adding a solution: the adopted electrolytic cell device is shown in figure 2, and is provided with two ion exchange membranes to divide the electrolytic cell into three reaction chambers; an anode 2 connected with the positive pole of the power supply is arranged in a reaction chamber at one end, and the reaction chamber is called an end anode chamber 7; a cathode 1 connected with a negative electrode of a power supply is arranged in the other reaction chamber and the middle reaction chamber, and the two reaction chambers are respectively called an end cathode chamber 9 and a middle cathode chamber 8; the ion exchange membrane between the end anode chamber and the middle cathode chamber is a cation exchange membrane 3, and the ion exchange membrane between the end cathode chamber and the middle cathode chamber is an anion exchange membrane 4. IrO is adopted as the inner electrode of the end anode chamber 7 2 ·Ta 2 O 5 Coating a titanium electrode; the electrode in the end cathode chamber 9 adopts a stainless steel electrode; the electrode of the middle cathode chamber 8 adopts a Cu electrode. The number of anodes in the end anode chambers is 1, the anodes are simultaneously connected with the anodes of two power supplies, and the cathodes of the end cathode chambers and the cathodes of the middle cathode chambers are respectively connected with the cathode of one of the power supplies.
1mol/L sulfuric acid and 0.5mol/L nitric acid are put into the end anode chamber 7, and 0.5mol/L sodium hydroxide aqueous solution is adopted in the end cathode chamber 9. Absorbing CO in the step (1) 2 Is introduced into the intermediate cathode compartment 8 at a rate of 50 ml/min.
(3) The power supply of the electrolytic cell device is switched on for electrolysis, and the electrolysis temperature is 40 ℃. After the power is switched on, the end anode chamber generates pure O 2 (ii) a Pure H is produced in the end cathode chamber 2 (ii) a The intermediate cathode compartment produces the reduction products methane and ethanol.
As shown in FIG. 2, the organic-rich solution electrolyzed in the middle cathode chamber 8 is separated from the organic reduction product and then introduced into the end cathode chamber 9 at a flow rate of 50ml/min, and CO is introduced into the solution in the end cathode chamber 2 An absorption device 10 for absorbing CO in the flue gas 2 The gas, absorbed solution, can be reused in the intermediate cathode compartment. Meanwhile, 2H is generated in the end anode chamber during the reaction 2 O-4e - →4H + +O 2 Water is consumed and water is replenished during the electrolysis process.
Example 3
(1) Carbon dioxide absorption: potassium carbonate solution is adopted to absorb gas containing 1 percent of carbon dioxide, and the concentration of potassium bicarbonate after absorption reaches 0.2mol/L.
(2) Setting an electrolytic cell device and adding a solution: the adopted electrolytic cell device is shown in figure 2, and is provided with two ion exchange membranes to divide the electrolytic cell into three reaction chambers; an anode 2 connected with the positive pole of the power supply is arranged in a reaction chamber at one end, and the reaction chamber is called an end anode chamber 7; a cathode 1 connected to the negative electrode of the power supply is provided in the other end reaction chamber and the middle reaction chamber, which are respectively referred to as an end cathode chamber 9 and a middle cathode chamber 8; the ion exchange membrane between the end anode chamber and the middle cathode chamber is a cation exchange membrane 3, and the ion exchange membrane between the end cathode chamber and the middle cathode chamber is also a cation exchange membrane 3. The inner electrode of the end anode chamber 7 adopts a graphite electrode; the electrode in the end cathode chamber 9 adopts a copper electrode; the electrode of the middle cathode chamber 8 adopts a Pd electrode. The number of anodes in the end anode chambers is 1, the anodes are simultaneously connected with the anodes of two power supplies, and the cathodes of the end cathode chambers and the cathodes of the middle cathode chambers are respectively connected with the cathode of one of the power supplies.
1mol/L phosphoric acid and 0.5mol/L hydrochloric acid are put into the end anode chamber 7, and 0.5mol/L ammonia water and 0.1mol/L ammonium sulfate solution are adopted in the end cathode chamber 9. Absorbing CO in the step (1) 2 Is introduced into the intermediate cathode compartment 8 at a rate of 20 ml/min.
(3) The power supply of the electrolytic cell device is switched on for electrolysis, and the electrolysis temperature is 40 ℃. After the power is switched on, pure Cl is generated in the end anode chamber 2 (ii) a Pure H is produced in the end cathode chamber 2 (ii) a The intermediate cathode compartment produces the reduction products formic acid and CO.
Separating the reduction product from the electrolyzed solution in the middle cathode chamber 8, introducing into the end cathode chamber 9 at a flow rate of 20ml/min, introducing CO into the solution in the end cathode chamber 2 An absorption device for absorbing CO in the flue gas 2 The gas, absorbed solution, can be reused in the intermediate cathode compartment.
Example 4
(1) Carbon dioxide absorption: the potassium carbonate, sodium carbonate and piperazine solution are adopted to absorb gas containing 15% of carbon dioxide, the concentration of potassium bicarbonate after absorption reaches 0.5mol/L, and the concentration of sodium bicarbonate reaches 0.7mol/L.
(2) Setting an electrolytic cell device and adding a solution: the cell and electrodes used were the same as in example 3.
1mol/L phosphoric acid and 0.5mol/L hydrochloric acid are put into the end anode chamber 7, and 0.5mol/L ammonia water and 0.1mol/L ammonium sulfate solution are adopted in the end cathode chamber 9. Absorbing CO in the step (1) 2 Is introduced into the intermediate cathode compartment 8 at a rate of 20 ml/min.
(3) The power supply of the electrolytic cell device is switched on for electrolysis, and the electrolysis temperature is 20 ℃. After the power is switched on, pure Cl is generated in the end anode chamber 2 (ii) a Pure H is produced in the end cathode chamber 2 (ii) a The intermediate cathode compartment produces the reduction products formic acid and CO.
Separating the reduction product from the electrolyzed solution in the middle cathode chamber 8, introducing into the end cathode chamber 9 at a flow rate of 20ml/min, introducing CO into the solution in the end cathode chamber 2 An absorption device for absorbing CO in the flue gas 2 The gas, absorbed solution, can be reused in the intermediate cathode compartment.
Example 5
(1) Carbon dioxide absorption: potassium carbonate solution is adopted to absorb gas containing 5 percent of carbon dioxide, and the concentration of potassium bicarbonate after absorption reaches 0.5mol/L.
(2) Setting an electrolytic cell device and adding a solution: the electrolytic cell used was the same as in example 2. The end anode chamber electrode adopts a glassy carbon electrode; the electrolysis in the end cathode chamber adopts a Zn electrode; the electrode of the middle cathode chamber adopts an Au electrode.
1mol/L phosphoric acid and 0.5mol/L sulfuric acid are put into the end anode chamber 7, and sodium sulfate is added as supporting electrolyte; the end cathode chamber 9 was made of 0.5mol/L potassium hydroxide +0.1mol/L potassium carbonate, and sodium hydrogen sulfate was added as a supporting electrolyte. Absorbing CO in the step (1) 2 Is introduced into the intermediate cathode chamber 8 at a rate of 20 ml/min.
(3) The power supply of the electrolytic cell device is switched on for electrolysis, and the electrolysis temperature is 80 ℃. After the power is switched on, the end anode chamber generates pure O 2 (ii) a Pure H is produced in the end cathode chamber 2 (ii) a The intermediate cathode compartment produces the reduction product formic acid.
Separating reduction products from the solution electrolyzed in the middle cathode chamber 8, introducing into the end cathode chamber 9 at a rate of 20ml/min, introducing CO into the solution in the end cathode chamber 2 An absorption device for absorbing CO in the flue gas 2 The gas, absorbed solution, can be reused in the intermediate cathode compartment.
Example 6
(1) Carbon dioxide absorption: potassium carbonate and piperazine solution are adopted to absorb gas containing 12% of carbon dioxide, and the concentration of potassium bicarbonate after absorption reaches 0.5mol/L.
(2) Setting an electrolytic cell device and adding a solution: the electrolytic cell used was the same as in example 2. An iridium oxide coating titanium electrode is adopted as an end anode chamber electrode; the electrolysis in the end cathode chamber adopts a titanium electrode; the electrode of the middle cathode chamber adopts a Cu electrode.
1mol/L sulfuric acid is put into the end anode chamber 7; the end cathode chamber 9 was filled with 1mol/L aqueous potassium carbonate solution. Absorbing CO in the step (1) 2 Is introduced into the intermediate cathode compartment 8 at a rate of 30 ml/min.
(3) The power supply of the electrolytic cell device is switched on for electrolysis, and the electrolysis temperature is 20 ℃. After the power is switched on, the end anode chamber generates pure O 2 (ii) a Pure H is produced in the end cathode chamber 2 (ii) a The intermediate cathode compartment produces the reduction product methane.
Separating the reduction product from the electrolyzed solution in the middle cathode chamber 8, introducing into the end cathode chamber 9 at a flow rate of 20ml/min, introducing CO into the solution in the end cathode chamber 2 An absorption device for absorbing CO in the flue gas 2 The gas, absorbed solution, can be reused in the intermediate cathode compartment.
Example 7
Essentially the same as example 2, except that: two anodes are arranged in the end anode chambers, the two anodes are respectively connected with the positive electrodes of two power supplies, and the negative electrodes of the two power supplies are respectively connected with the cathodes of the end cathode chambers and the cathodes of the middle cathode chambers, as shown in fig. 3.
Example 8
Essentially the same as example 3, except that: two anodes are arranged in the end anode chambers, the two anodes are respectively connected with the positive electrodes of two power supplies, and the negative electrodes of the two power supplies are respectively connected with the cathodes of the end cathode chambers and the cathodes of the middle cathode chambers, as shown in fig. 3.

Claims (9)

1. A method for capturing, reducing carbon dioxide and co-producing oxygen or chlorine, comprising the steps of:
(1) Carbon dioxide absorption: absorbing CO in flue gas by using solution containing hydroxide or/and carbonate 2 A gas to form an absorption solution;
(2) The following procedure was used, the cell set up and the solution added:
the electrolytic cell device is provided with two ion exchange membranes, and the electrolytic cell is divided into three reaction chambers; an anode connected with the positive pole of a power supply is arranged in a reaction chamber at one end, and the reaction chamber is called an end anode chamber; a cathode connected with a negative electrode of a power supply is arranged in the reaction chamber at the other end and the middle reaction chamber, and the two reaction chambers are respectively called an end cathode chamber and a middle cathode chamber; the ion exchange membrane between the end anode chamber and the middle cathode chamber is a cation exchange membrane, and the ion exchange membrane between the end cathode chamber and the middle cathode chamber is a cation exchange membrane or an anion exchange membrane; adding an alkali solution into the end cathode chamber, adding an absorption solution into the middle cathode chamber, and adding an acid solution into the end anode chamber;
the cathode arranged in the middle cathode chamber is one of Cu, zn, pb, ag, au and Pt metal electrodes or alloy among the Cu, zn, pb, ag, au and Pt metal electrodes;
(3) And switching on a power supply of the electrolytic cell device to carry out electrolysis, and respectively collecting gas generated in the end anode chamber and the end cathode chamber and gas or/and liquid reduction products generated in the middle cathode chamber.
2. The method for capturing, reducing and co-producing carbon dioxide and oxygen or chlorine as claimed in claim 1, wherein the acid solution is one or a mixture of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid in any proportion; the alkali solution is one or a mixture of more of aqueous solution of alkali metal hydroxide, aqueous solution of alkali metal carbonate, aqueous solution of alkali metal bicarbonate, ammonia water, ammonium carbonate, ammonium bicarbonate and aqueous solution of ammonium sulfate in any proportion.
3. The method of capturing, reducing carbon dioxide and CO-producing oxygen or chlorine as claimed in claim 1, wherein the CO in the flue gas 2 The gas is in any concentration, and the concentration of the bicarbonate in the absorption solution is more than 0.1mol/L.
4. The process for capturing, reducing carbon dioxide and CO-producing oxygen or chlorine as claimed in claim 1, wherein the electrolyzed solution of the end cathode chamber is recovered for use in step (1) for absorbing CO in flue gas 2 A gas.
5. The method for capturing and reducing carbon dioxide and coproducing oxygen or chlorine as claimed in claim 1, wherein the absorption solution is continuously introduced into the intermediate cathode chamber, the solution electrolyzed in the intermediate cathode chamber is introduced into the end cathode chamber after separation of the reduction product, and the solution electrolyzed in the end cathode chamber is used for absorbing CO in the flue gas in the step (1) 2 A gas.
6. The method for capturing, reducing carbon dioxide and co-producing oxygen or chlorine as claimed in claim 1, wherein KCl and K are further added to the solution in each reaction chamber 2 SO 4 、KClO 4 Phosphate, sodium chloride, sodium sulfate, KHSO 4 、NaHSO 4 One or more of sodium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, quaternary ammonium salt, choline chloride, propylene carbonate, N-methylpyrrolidone, diethyl carbonate and acetonitrile are used as supporting electrolytes.
7. The method for capturing, reducing carbon dioxide and CO-producing oxygen or chlorine as claimed in claim 1, wherein step (1) is used for absorbing CO in flue gas 2 The solution of gas also contains an absorption enhancer.
8. The method for capturing, reducing carbon dioxide and co-producing oxygen or chlorine as claimed in claim 1, wherein the anode in the end anode chamber is iridium oxide coated titanium electrode, irO 2 ·Ta 2 O 5 Coating a titanium electrode, a glassy carbon electrode or a graphite electrode; the cathode in the end cathode chamber adopts one of a titanium electrode, a stainless steel electrode, a graphite electrode, cu, zn, pb, ag, au and Pt metal electrodes or an alloy of the titanium electrode, the stainless steel electrode and the graphite electrode.
9. The method of capturing, reducing carbon dioxide and co-producing oxygen or chlorine as claimed in claim 1, wherein the number of anodes in the end anode chamber is one or two; when one anode is arranged in the end anode chamber, the anode is simultaneously connected with the anodes of two power supplies, and the cathodes of the end cathode chamber and the middle cathode chamber are respectively connected with the cathode of one of the power supplies; when two anodes are arranged in the end anode chamber, the two anodes are respectively connected with the anodes of the two power supplies, and the cathodes of the two power supplies are respectively connected with the cathode of the end cathode chamber and the cathode of the middle cathode chamber.
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Publication number Priority date Publication date Assignee Title
CN114645290B (en) * 2022-02-25 2023-06-30 东南大学 CO (carbon monoxide) 2 Synchronous conversion system and method for trapping and electric regeneration
CN114870602B (en) * 2022-05-31 2023-08-22 江苏科技大学 Carbon capture system for regulating pH value based on potassium carbonate absorbent combined with capacitive deionization technology
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102181876A (en) * 2011-03-30 2011-09-14 昆明理工大学 Method and device for preparing carbon monoxide through electrochemical catalytic reduction of carbon dioxide
CN103160849A (en) * 2011-12-12 2013-06-19 清华大学 Carbon dioxide electrochemical reduction conversion utilization method
CN105420751A (en) * 2014-09-23 2016-03-23 中国科学院大连化学物理研究所 Method for preparing hydrocarbon through electrochemical reduction of carbon dioxide
CN108286054A (en) * 2018-02-01 2018-07-17 昆明理工大学 A kind of diaphragm of electrolyzer and methods for using them of electrolysis carbon dioxide carbon monoxide
CN110983357A (en) * 2019-12-04 2020-04-10 昆明理工大学 Three-chamber diaphragm electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide and simultaneously producing chlorine and bicarbonate as byproducts
CN111575732A (en) * 2020-05-28 2020-08-25 昆明理工大学 Electrochemical preparation method of phosgene synthesis raw material
CA3112140A1 (en) * 2020-03-24 2021-09-24 Evonik Functional Solutions Gmbh Improved process for preparing sodium alkoxides
CN113549929A (en) * 2021-08-10 2021-10-26 北京化工大学 Method and system for realizing hydrogen production, organic matter oxidation, carbon dioxide absorption-desorption and hydroxide regeneration

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102181876A (en) * 2011-03-30 2011-09-14 昆明理工大学 Method and device for preparing carbon monoxide through electrochemical catalytic reduction of carbon dioxide
CN103160849A (en) * 2011-12-12 2013-06-19 清华大学 Carbon dioxide electrochemical reduction conversion utilization method
CN105420751A (en) * 2014-09-23 2016-03-23 中国科学院大连化学物理研究所 Method for preparing hydrocarbon through electrochemical reduction of carbon dioxide
CN108286054A (en) * 2018-02-01 2018-07-17 昆明理工大学 A kind of diaphragm of electrolyzer and methods for using them of electrolysis carbon dioxide carbon monoxide
CN110983357A (en) * 2019-12-04 2020-04-10 昆明理工大学 Three-chamber diaphragm electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide and simultaneously producing chlorine and bicarbonate as byproducts
CA3112140A1 (en) * 2020-03-24 2021-09-24 Evonik Functional Solutions Gmbh Improved process for preparing sodium alkoxides
CN111575732A (en) * 2020-05-28 2020-08-25 昆明理工大学 Electrochemical preparation method of phosgene synthesis raw material
CN113549929A (en) * 2021-08-10 2021-10-26 北京化工大学 Method and system for realizing hydrogen production, organic matter oxidation, carbon dioxide absorption-desorption and hydroxide regeneration

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